CH653033A5 - POLYHETEROCYCLIC THIENO (2,3-B) COMPOUNDS, THEIR PRODUCTION AND THEIR USE. - Google Patents

Description

The invention relates to polyheterocyclic thieno 2,3-b io compounds, their preparation and their use as optical brighteners.

A first subject of the invention is therefore the compounds of the formula

(I)

HY-

cyclized with elimination of water.

3. A process for the preparation of compounds of the formula (I) according to claim 1, in which Y is oxygen or sulfur, characterized in that an alkali metal sulfide or hydrosulfide with a compound of the formula

Shark

20 wherein X is -O- or -S-, Y -O-, -S- or -NR- and R are hydrogen or Ci-4-alkyl, and the rings A and B may optionally be further substituted by non-chromophoric substituents.

Preferred compounds of formula (I) correspond to formula 25

CHO

and a compound of the formula

(VII),

wherein shark is chlorine, bromine or iodine and Y '-O- or -S-, successively in any order, or simultaneously.

4. A process for the preparation of compounds of the formula (I) according to claim 1, in which Y is oxygen or sulfur, characterized in that a disulfide of the formula in which m and n are each, independently of one another, an integer from 0-3,

Ri and R2 each independently of one another Ci-4-alkyl, 3s halogen, Ci-4-alkoxy, cyano, -CONH2, -COOR3, methylsulfonyl or optionally phenyl monosubstituted by halogen, Ci-4-alkyl or Ci-4-alkoxy or if m or n is 2 and the corresponding substituents Ri or R2 are ortho to one another, the two ortho radicals Ri or the two ortho radicals R2, together are the atoms and atomic groups necessary to form a fused-on benzo ring, or if m or n = 1, Ri or R2 is also the group of the formula

U),

(VIII)

with an aldehyde of the formula (VI) under reductive conditions.

5. A process for the preparation of compounds of formula (I) according to claim 1, wherein Y is -NR- and R C1-4-alkyl, characterized in that compounds prepared by the process according to claim 2, wherein Y is -NH- , alkylated to introduce an N-linked Ci-4 alkyl group.

6. Use of the compounds of formula (I) according to claim 1 for the optical brightening of non-textile substrates.

7. The optically brightened materials according to the use according to claim 3.

8. Aqueous brightener preparations which are characterized by a content of compounds of the formula (I) according to claim 1.

50 R3 is hydrogen or Ci-4-alkyl, Rio halogen or Cw-alkyl and a is 0 or 1, and if two ortho-permanent symbols Ri or two ortho-permanent symbols R2 form a fused-on benzo ring, this may be halogen or Ci-4-alkyl can be monosubstituted. 55 If the index m or n stands for a number which is greater than 1 and the corresponding substituents are not condensed to form a benzo ring, then the symbols Ri and the symbols R2 can each have the same meaning or different meanings, Preferably, then at most one of the substituents R 1 or at most one of the substituents R 2 is one of the electron acceptors mentioned; particularly preferably none of the substituents R 1 and R 2 mean an electron acceptor.

Halogen represents fluorine, chlorine or bromine, advantageously 65 chlorine or bromine, preferably chlorine. The methoxy group is preferred among the Ci-4-alkoxy groups occurring in the molecule. Among the Ci-4 alkyl radicals as R or R3, the methyl and ethyl groups are preferred; of the rest of the

3rd

653033

The methyl group is preferred for Ci-4-alkyl residues occurring in the molecule. If two mutually ortho symbols Ri and R2 form fused benzo rings, then this is preferably unsubstituted; the condensed ring on ring A is preferably in positions 7 and 8. The index m is preferably m ', i.e. for 0.1 or 2, in particular for m ", i.e. for 0 or 1. The index n preferably stands for n ', i.e. for 0.1 or 2, particularly preferably for 0. The index a preferably stands for 0.

Ri is preferably Ri, i.e. for Ci-4-alkyl, Ci-4-alkoxy and / or chlorine, or if m = 2 and the two symbols are ortho to one another, these can form the atoms and atomic groups necessary to form a fused-on benzo ring.

R2 is preferably R2 ', i.e. for Ci-4-alkyl, Ci-4-alkoxy and / or chlorine, or if n = 2 and the two symbols Ry are ortho to one another, these can also form the atoms and atomic groups necessary to form a fused-on benzo ring.

Ri or Ri is particularly preferably Ri -, i.e. for methyl or chlorine.

R2 or R2 'particularly preferably stands for R2 », i.e. for methyl or chlorine.

The symbol X preferably stands for -O-.

The symbol Y preferably stands for Y ', i.e. for -O- or -S-, especially for -S-.

Preferred compounds of the formula (Ia) correspond to the formula

Particularly preferred compounds of the formula (Ia) or (II) correspond to the formula

Elf1 $ OLjnC ^ 12 ("D

r13

wherein R11 is hydrogen, chlorine or methyl, R12 is hydrogen or methyl and R13 is hydrogen or methyl.

Particularly preferred compounds of the formula (III) correspond to the formula

Shark ■ CHO

and a compound of the formula

(VI)

15

(VII)

wherein shark is chlorine, bromine or iodine, preferably chlorine or bromine, in succession in any order, or simultaneously, or c) for the preparation of compounds of the formula (I) in which Y is oxygen or sulfur, a disulfide of the formula

(VIII)

reacted with an aldehyde of the formula (VI) under reductive conditions and, if appropriate, in the reaction products of process variants a), b) and c) on the rings A and / or B, any substituents present are replaced by other, in a manner known per se and / or, if Y is -NH-, this is optionally alkylated for the introduction of an N-linked Ci-4-alkyl group.

The ring closure according to process variant a) is advantageously carried out in a manner known per se by heating in an inert solvent, such as Sulfolane, toluene, chlorobenzene, dichlorobenzene or trichlorobenzene, preferably in the temperature range of 100-290 ° C, in particular

130-240 ° C, in the presence of an acid catalyst, e.g. Boric acid or paratoluenesulfonic acid. For the ring closure of compounds in which Y is oxygen, higher temperatures are generally preferred than for Verbin-40 in which Y is sulfur. The reaction time can vary widely depending on the compound, solvent and temperature and is generally in the range of 1-24 hours, preferably 2-4 hours.

The amides of the formula (V) can be prepared in a manner known per se, primarily by reacting a compound of the formula

(IX)

wherein Ri i 'is hydrogen or chlorine.

The process for the preparation of the compounds of the formula (I) is characterized in that a) a corresponding compound of the formula in which R4 is the carboxylic acid group, a carboxylic acid ester group or a —CO-Hal group, with a compound of the formula

(V)

cyclized with elimination of water or b) an alkali metal sulfide or hydrosulfide with a compound of the formula to prepare compounds of the formula (I) in which Y is oxygen or sulfur

(X)

60 wherein the ring B in formula (X) expediently has no carboxy group.

As carboxylic ester groups R4, primarily methyl and ethyl esters come into question.

The reaction of the compound of formula (IX) with the compound of formula (X) is carried out in a manner known per se, expediently by heating, preferably in a suitable inert solvent, if appropriate in the presence of a suitable auxiliary (e.g. an acidic catalyst)

653033

sators such as Boric acid. The rest -CO-Hal preferably represents -CO-Cl. The acid chloride (R.4 means -CO-Cl) is preferably used; the acid chloride is conveniently obtained from the corresponding carboxylic acid (R.4 means carboxy) by reaction with thionyl chloride in an inert solvent, e.g. Chloroform, toluene or chlorobenzene, at temperatures between 40 and 140 ° C, preferably between 50 and 110 ° C. The amidation reaction of the compounds of the formula (IX) with the amines of the formula (X) takes place in a manner known per se, advantageously in an inert solvent (for example as mentioned above) in a temperature range advantageously between room temperature and 200 °, where if R4 means carbonyl chloride, the reaction can take place at lower temperatures than when R4 means the carboxy group or the carboxylic acid ester group. The first reaction stage is advantageously completed at temperatures of 80-200 ° C, preferably 120-180 ° C (reaction time about Vi h to 8 h). If desired, the amide can be isolated from the reaction mixture and dried before the cyclization; According to the method described by SEHA and WEIS in Helvetica Chimica Acta 63 (1980), 413, the chlorination of the carboxy group, the amidation and the ring closure are advantageously carried out in a single operation.

If the ring A contains a carboxy group, this can also be converted into a corresponding benzoxazole residue at the same time; If desired, ester groups present in rings A and / or B can be converted into acid groups in a manner known per se, e.g. by refluxing in an inert solvent in the presence of aqueous alkali. Rings A and B preferably have no carboxy groups and also no carboxylic acid derivatives which could compete with the reaction in an undesired manner.

The reaction b) is also conveniently carried out in a manner known per se in a suitable solvent, e.g. Dimethylformamide, N-methylpyrrolidone or ethanol. The alkali metal sulfide or hydrosulfide is advantageous first with one of the compounds of the formulas (VI) and (VII) and then with the other of these two compounds, with the formation of the thioether of the formula

CH,

CHO

implemented (advantageously at 0-30 ° C, preferably 1-2 hours); after addition of a base (preferably a tertiary amine, especially triethylamine) the ring closure takes place, advantageously at 80-160 ° C, preferably 140-160 ° C, in 1-6 hours. If desired, the reaction of compounds (VI) or (VII) with the sulfide or hydrosulfide in an aqueous two-phase system (e.g. water and a chlorinated hydrocarbon, especially water / dichloromethane, water / dichloroethane or water / chlorobenzene) in the presence of a phase transfer catalyst e.g. a customary aliphatic, quaternary ammonium salt (in particular a tetraalkylammonium halide, preferably N-butyltrimethylammonium chloride) or a customary crown ether.

The reaction c) is carried out in a manner known per se, expediently in an organic solvent, analogously to reaction b), a metal, such as, for example, advantageously being the reducing agent. Sodium or zinc is used. The disulfides of the formula (VIII) can be prepared by reacting compounds of the formula (VII) with an alkali metal disulfide under analogous conditions, such as the reaction of the compounds of the formula (VII) with the sulfides in process variant b).

The reaction products can be separated from the reaction mixture in a manner known per se, e.g. by cooling and filtering; if desired the compounds can e.g. can be cleaned by recrystallization or redissolution.

If desired, substituents present in the reaction product can be replaced by others in a manner known per se; for example a compound in which Y is -NH- alkylated in a manner known per se for introducing an alkyl radical R or; if a bromine atom is present as a substituent in the rings A or B, this can e.g. be replaced with copper (I) cyanide (e.g. in quinoline) by a nitrile group; If desired, carboxy groups can be esterified or reacted with corresponding orthoaminophenols to introduce the rest (a); If desired, nitrile groups can be converted to carbamoyl groups and carbamoyl or carboxylic ester groups can be saponified to carboxy groups if desired.

The compounds of the formula (IX) are a particular subject of the invention; the process for their preparation is characterized in that a compound of the formula (VI) is reacted with a corresponding alkyl thioglycolic ester and, if desired, the carboxylic acid ester group is then saponified and, if appropriate, chlorinated to the acid chloride in the customary manner. The reaction with the thioglycolic acid ester (preferably methyl thioglycolic acid) is advantageously carried out in a solvent under basic conditions and under mild temperature conditions; the hydrolysis of the ester group to the carboxy group is advantageously carried out in a manner known per se by heating in the presence of alkali and subsequent acidification with an inorganic acid (preferably hydrochloric acid).

The compounds of the formulas (VI), (VII) and (X) are known or can be prepared from known products by methods known per se.

The compounds of formula (I), and in particular the preferred ones, have a brightening character and serve for the optical brightening of textile and non-textile substrates, in particular those which are free from water-solubilizing groups, for the optical brightening of synthetic and semisynthetic, fiber-forming polymers , in particular of polyamide, polypropylene, polyester, cellulose-2 Vi-acetate and cellulose triacetate are suitable; polyester is particularly preferably optically brightened. The substrates can be optically lightened in bulk (in particular in the spinning melt or spinning solution) prior to shaping, or the fiber material already formed can be optically lightened from an aqueous medium, the optical brighteners free of water-solubilizing groups expediently being present as an aqueous dispersion. The fibrous material can be in any suitable form of processing, e.g. as loose fibers, filaments, threads, strands, fabrics, knitted fabrics, tufted goods, non-woven fabrics or felts. Application from an aqueous medium is preferred, in particular exhaust processes and thermosol processes, where the treatment liquor can contain customary additives, such as Carriers, dispersants, undressing aids, anti-foaming agents and / or anti-crease agents (when optically brightened in nozzle dyeing apparatus); It should be particularly emphasized that the optical brighteners according to the invention can also be used to lighten optically without the addition of carrier.

Another object of the invention are aqueous brightener preparations, which contain compounds of the

4th

s

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

653033

Formula (I), if appropriate in addition to other additives customary in corresponding brightener preparations, are characterized, in particular aqueous dispersions of water-solubilizing groups-free compounds of the formula (I) and suitable dispersants such as e.g. ethoxylated fatty alcohols or alkylphenols and / or sulfonated aliphatic esters. A special aspect of this object of the invention are corresponding brightener preparations which, in addition to compounds of the formula (I), contain, as optically brightening active substance, further optically brightening active substances which are compatible with the compounds of formula (I), in particular optical brighteners as in the German ones Interpretation documents 1 040 555.1 235 255.1 282 021.1 112 072 and 1273 479, in FR-PS 1 154 529 and in German Offenlegungsschriften 2 247 791 and 2 602 750. The weight ratio of the compounds of formula (I) to the other optical brighteners in such preparations is advantageously 1: 9 to 9: 1. These brightener mixtures [where the compounds of the formula (I) are advantageously free from water-solubilizing groups] are advantageously in the form of aqueous dispersions which advantageously contain conventional dispersants, as mentioned above. These dispersions can e.g. for concentrated commercial forms, have a brightener content of advantageously 1 to 20% by weight; the concentration is correspondingly lower in stock dispersions.

In the following examples, the temperatures are given in degrees Celsius.

example 1

A suspension of 15.5 g of thieno [3,2-b] benzofuran-2-carboxylic acid and 16.9 g of thionyl chloride in 150 ml of chloroform and 1 ml of dimethylformamide is refluxed for 5 hours, after which the reaction mixture is filtered; after removal of the solvent from the filtrate, the thieno [3,2-b] benzofuran-2-carboxylic acid chloride is obtained as a brown solid product. 5.1 g of this acid chloride are added in portions over the course of 30 minutes to a mixture of 7.2 g of 2-aminothiophenol, 50 ml of toluene and 5 ml of pyridine, cooled with an ice bath, with stirring; after the addition has ended, the reaction mixture is stirred for a further 17 hours at room temperature, then cooled and filtered; the filter residue is washed with ligroin and gives the amide of the formula

CO-NH

(i)

A mixture of the amide of formula (1), boric acid and sulfolane is heated under nitrogen to 230 ° C. in the course of 3 hours, after which it is kept at 230 ° C. for a further hour; it is then cooled and poured into 60 ml of water, whereupon a dark brown product precipitates, which is filtered off, washed with water, dried and crystallized from cellosolve; for further purification, the product is chromatographed on a silica gel column and finally recrystallized from chlorobenzene, whereupon the benzothiazole compound of the formula

(2)

20th

in the form of light yellow needles with melting point 249-250 ° C.

The thieno [3,2-25 b] benzofuran-2-carboxylic acid used as the starting compound is prepared as follows:

A mixture of 27.1 g of 3-chloro-2-formyl-benzofuran (Chemical Abstracts 59 15239b), 19.1 g of thioglycolic acid methyl ester, 150 ml of pyridine and 18.9 g of water is stirred and cooled to 15 ° C .; 30 ml of triethylamine are then added dropwise with stirring over the course of 15 minutes at 15 ° C. The reaction mixture is then stirred at room temperature for 1 hour, then at 45 ° C. for 1 hour and then cooled below 20 ° C., while 30 ml of a 50% potassium hydroxide solution are added dropwise over the course of 35 minutes. The reaction mixture is stirred at room temperature for 1 hour and then poured into 1500 ml of water and filtered. The solid product is refluxed for 4 hours with a mixture of 6.75 g of potassium hydroxide and 40-100 ml of ethanol, 25 ml of water are added and the mixture is refluxed for a further hour; then the reaction mixture is poured into 250 ml of hot water and the mixture obtained is heated to boiling temperature and filtered. The filtrate obtained is acidified with hydrochloric acid and the precipitated thieno [3,2-b] benzofuran-2-carboxylic acid is filtered off, washed with water and dried.

50

in the form of a brown solid product.

Examples 2 to 14 In the following table are compounds of the formula

(3)

listed, which are prepared analogously as described in Example 1 and by the substituents Rw-Rn,

Hetero atoms X and Y and the melting point are marked.

653033

6

example

Rl4

Ris

Rló

Marg

X

Y

Melting point in ° C

2nd

H

CHs

H

H

O

s

198-9

3rd

H

Cl

H

H

O

s

222

4th

H

H

H

-OCH3

O

0

187

5

H

H

H

H

0

0

239

6

CHs

Cl

CHs

H

0

0

253-5

7

CHs

Cl

CH3

H

0

s

237-9

8th

H

H

H

H

S

s

200-1

9

H

H

H

H

S

0

207-8

10th

H

H

H

Br

S

0

196-202

11

H

H

H

-OCH3

s

0

212

12

H

H

Br

H

s

0

248-58

13

H

H

Br

-OCH3

s

0

278-85

14

H

H

CH3

H

0

s

220-22

Example 15 20 the reaction mixture is cooled and with 50 ml of water

A mixture of 8 g of 7-methyl-thieno [3,2-b] benzofuran-2 was added. The tar-like product is chromatographed on aluminum oxide carboxylic acid, 4.2 g of 2-amino-5-methylphenol, 0.5 g of boric acid and then acetone, isopropanol and and 20 ml of sulfolane are first at 160-170 ° C and then Recrystallized benzene, making the product of

Gently stirred for 3 hours at 230-240 ° C under nitrogen. Afterwards formula '

(4)

as a salmon-colored, solid product with a melting point.

205-206 ° C.

The 7-methyl-thieno [3,2- Examples 16 to 27 used as the starting product

b] Benzofuran-2-carboxylic acid is, analogously to the thieno [3,2-35]. In the following table, further b] benzofuran-2-carboxylic acids according to the invention are the compounds of the formula described in Example 1

R

(5)

'20

listed, which are prepared analogously to Example 15 and are characterized by the substituents R18-R22, the heteroatoms X and Y and the melting points.

example

R18

Rl9

R20

R21

R22

X

Y

Melting point in ° C

16

H

H

H

H

cm

0

0

223

17th

H

CHs

H

CHs

H

0

0

214-5

18th

H

H

CHsO

H

H

0

0

196-7

19th

H

CHs

H

CH3

cm

0

0

245

20th

H

H

H

CHs cm

0

0

266

21st

H

CHs

H

Cl

H

0

0

254-5

22

(-CH =>

(°) -

H

H

H

0

0

241

23

H

H

H

H

0

0

228-9

24th

H

H

H

H

SO2CH3

0

s

315

25th

H

H

H

H

ocm

0

s

224-6

26

H

H

H

H

H

0

NH

305-6

27th

H

H

H

H

H

s

NH

264-5

Example 28 65 Stirred for 30 min. Then 3.2 g of 2-amino

5 g of thieno [3,2-b] benzofuran-2-carboxylic acid, 30 ml of N-methiophenol are added and the reaction mixture is heated in ethylpyrrolidone and 3 g of thionyl chloride are heated to 140 ° C. for 2 hours and then 2 more Hours.

mixed at 0-10 ° C and the mixture is kept at room temperature at this temperature, after which it is cooled;

7

653033

the precipitate is filtered off with ethanol, washed and recrystallized from xylene, whereby the compound of formula (2) of Example 1 is obtained in the form of light yellow needles with a melting point of 248-249 ° C.

Example 29

A mixture of 6.5 g of 6,7-dimethyl-2-methoxycarbonylthieno [3,2-b] benzofuran, 3.0 g of orthoaminophenol and 0.1 g of boric acid is gradually heated to 180 ° C. under nitrogen. The reaction mixture is kept at 180 ° C. for 30 minutes and then further heated to 220-230 ° C. Kept at 220-230 ° C for a further 1 hour; then it is cooled to 100 ° C. and 10 ml of methanol are slowly added. The brown, solid product is filtered and purified by chromatography on an alumina column and then crystallized from cellosolve to give the compound of formula

example

R23

R24

R25

Melting point in ° C

29

CHs

H

CHs

242-44

31

H

CHs

CHs

236-39

CH ß

in the form of light yellow needles, melting point 223-225 ° C.

Examples 30 and 31 In the following table are the compounds of the formula

Example 32

A solution of 4.1 g of sodium sulfide dihydrate in 200 ml of water is added over the course of 15 minutes to a solution of 6.5 g of 3,5-dichloro-2-formylbenzofuran in 50 ml of dimethylformamide at 0-5 ° C. admitted. The reaction mixture is stirred for a further 30 min at 0-5 ° C and in the course of 15 min at 0-10 ° C a solution of 6.6 g of 2-chloromethylbenzothiazole (Chem. Abs. 49 13223e) in 80 ml of dimethyl-15 formamide are added dropwise, after which the reaction mixture is stirred for a further hour at room temperature. Then 6.1 g of triethylamine are added and the reaction mixture is stirred at room temperature for a further 30 minutes and then refluxed for one hour; then

20 the mixture is cooled and poured into water; the (6) solid precipitate is filtered off, washed thoroughly with water, dried and recrystallized from cellosolve, whereby the compound of Example 3 is obtained as a light yellow, solid product.

25 The 3,5-dichloro-2-formyl-benzofuran used as the starting product is produced from 5-chloro-coumaronone in an analogous manner to the 3-chloro-2-formyl-benzofuran (cf. Chem. Abs. 59 15239d).

30 Examples 33-39

The following table shows further compounds of the formula according to the invention

R,

/ U

sN-

(8th)

(7)

R

26

35

R

èco

30th

28

R

40

29

listed, which are prepared analogously to Example 29, and are characterized by the substituents R23, R24 and R25 and the melting points.

listed, which are prepared analogously to that described in Example 32 and are characterized by the substituents R26-R30, the heteroatom Y and the melting point.

Example R20

R27

R28

R29

R30

Y melting point in ° C

33

CHs

H

CHs

H

H

S

195-6

34

CHs

H

CHs

H

H

O

213

35

H

CHs

H

CHs

H

0

208-9

36

H

Cl

H

CHs

H

s

214-5

37

H

CHs

H

CHs

CHs

0

178-9

38

H

H

H

CHs

CHs

0

199-200

39

H

(CHs) sC

H

H

H

0

239

Example 40

A mixture of 1.85 g of the compound according to the example, the reaction mixture was cooled and the solid precipitate, 27.30 ml of dioxane, 1 ml of a 30% strength sodium hydroxide solution, filtered off, washed with ethanol, dried and made from iso-solution and 3.05 g of dimethyl sulfate is recrystallized for 3 hours at room temperature- 60 propanol, whereby the compound of the temperature and then stirred for 2 hours under reflux; then formula

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8th

in the form of a light yellow, solid product with a melting point of compounds of the formula 247-251 ° C.

^ ^ ^ .S

Example 41

Analogously to that described in Example 40, the compound of the formula is listed from the compound according to Example 26, which, analogously to Example 42, is prepared (10) 10 and is characterized by the substituents R31 and R32 and by the melting point.

obtained with melting point 185-187 ° C.

Example 42

A mixture of 1.5 g of the compound according to Example 12, 0.7 g of copper (I) cyanide and 20 ml of quinoline is refluxed for 17 hours, then cooled and poured into a mixture of 20 ml of concentrated hydrochloric acid and 20 poured ml of water. This mixture is then heated to 70 ° C. for 30 minutes, then cooled and the solid product is filtered off, washed with water, dried, extracted with hot xylene and finally crystallized from a mixture of dimethylformamide and water and then from butanol, whereby the compound of formula

example

R31

R32

Melting point in ° C

43

H

CN

273-4

44

NC

OCH3

> 360

20th

25th

in the form of a dark yellow, solid product with a melting point> 330 ° C.

Examples 43 and 44 40

In the following table there are 2 more according to the invention

Example 45

A mixture of 6.6 g of thieno [3,2-b] benzothiophene-2,6-dicarboxylic acid, 150 ml of toluene, 11.9 g of thionyl chloride and 1 ml of dimethylformamide is refluxed for 3 hours and then cooled; the precipitate is filtered off, washed with petroleum ether and dried. 6.6 g of the dried solid product is added in portions to an ice-cooled mixture of 4.6 g orthoaminophenol, 40 ml toluene and 16.5 ml pyridine. This mixture is stirred for 3 hours at room temperature and then refluxed for 30 minutes, after which it is cooled and then enough ethanol is added to granulate the precipitate, after which the solid diamide is filtered off and dried.

A mixture of 3.7 g of this solid diamide, 0.5 g of boric acid and 15 ml of sulfolane is heated under nitrogen in the course of 3 hours to 230 ° C. and then kept at 230 ° C. for a further hour, after which it is heated up Is cooled to 90 ° C., mixed with 50 ml of water and then cooled further to room temperature; the product is filtered and dried, then recrystallized from chlorobenzene, nitrobenzene and orthodichlorobenzene to give the compound of formula

with melting point 350 ° C.

Example of use A

8 g of a polyester fabric (“terylene”) are padded through 50 ml of an aqueous liquor containing 120 mg of the compound of the formula (2) according to Example 1 and 75 mg of an ethoxylated di-tert.butylphenol and up to an 80% strength Squeezed dry weight gain. The compound of formula (2) from Example 1 is used in the form of a 0.1% aqueous dispersion which contains a sulfonated aliphatic ester and a fatty alcohol ethoxylated with 10 mol of ethylene oxide as the dispersant. The padded fabric is thermally insulated at 190 ° C for 30 seconds. The fabric treated in this way is lightened brilliant white.

Example of use B

5 g of a polyester fabric (“terylene”) are added at 40 ° C. to 200 ml of an aqueous liquor which contains 50 mg of the compound of the formula (4) according to Example 15 and 200 mg of a castor oil which is ethoxylated with 30 mol of ethylene oxide, 50. The compound of formula (4) according to Example 15 is added to the whitening bath in the form of a 0.1% aqueous dispersion (analogous to Example A). The temperature of the lightening bath is raised to 95-98 ° C. in the course of 30 minutes with constant mechanical movement of the tissue and then kept at 95-98 ° C. for a further 45 minutes. The tissue is then removed from the bath, rinsed thoroughly with water and dried in a stenter at 80 ° C. The fabric treated in this way is lightened brilliant white.

60

Example of use C

5 g of a polyester fabric (“terylene”) is continuously agitated in a closed vessel with an aqueous mixture which contains 75 mg of the compound according to Example 3 and 75 mg of a 65 emulsified mixture of isomeric trichlorobenzenes at 100 ° C. for 45 minutes. The compound of Example 3 is used in the form of a 0.1% aqueous dispersion (analogous to Example A). The tissue will

then removed from the jar, washed thoroughly with water and dried at 80 ° C in a tenter. The fabric treated in this way is lightened brilliant white.

Example of use D

The procedure is as described in use example A, but instead of the 120 mg compound of the formula (2)

9 653033

Mixture of 60 mg of the compound of the formula (2) according to Example 1 above and 60 mg of 4,4'-bis (β-ethoxycarbonyl-vinyl) stilbene [= 'compound of the formula (4) from Example 2 of DE-OS 2 602 750] a. The two brighteners are used in the form of a 0.1% dispersion of the brightener mixture (analogous to example A).

Analogously to that described in Application Examples A-D, the rest of the compounds according to Examples 1-45 are used in each case.

6

Claims (2)

653033 2nd PATENT CLAIMS 1. Compounds of the formula 9. Aqueous dispersions according to claim 8, which contain, in addition to water-solubilizing groups, optical brighteners of the formula (I) according to claim 1 at least one dispersant. (I) wherein X is -O- or -S-, Y -O-, -S- or -NR- and R are hydrogen or Ci-4-alkyl, and the rings A and B are optionally further substituted by non-chromophoric substituents. 2. A process for the preparation of the compounds of formula (I) according to claim 1, characterized in that a corresponding compound of the formula ■ 0 ") ®